Mechanism of RuO2 Crystallization in Borosilicate Glass: An Original in Situ ESEM Approach

被引：32

作者：

Boucetta, Hassiba ^{[1
]}

Podor, Renaud ^{[3
]}

Stievano, Lorenzo ^{[2
]}

Ravaux, Johann ^{[3
]}

Carrier, Xavier ^{[4
]}

Casale, Sandra ^{[4
]}

Gosse, Stephane ^{[5
]}

Monteiro, Amelie ^{[1
]}

Schuller, Sophie ^{[1
]}

机构：

[1] CEA Marcoule, DEN DTCD SECM LDMC, F-30207 Bagnols Sur Ceze, France

[2] Univ Montpellier 2, ICG AIME UMR CNRS 5253, F-34095 Montpellier, France

[3] Inst Chim Separat Marcoule, UMR CEA CNRS UM2 ENSCM 5257, F-30207 Bagnols Sur Ceze, France

[4] UPMC Univ Pierre & Marie Curie, Lab React Surface, F-75005 Paris, France

[5] CEA Saclay, DEN DPC SCCME LM2T, F-91191 Gif Sur Yvette, France

来源：

INORGANIC CHEMISTRY | 2012年 / 51卷 / 06期

关键词：

PLATINUM-GROUP-METALS; SODA-SILICATE MELTS; LEVEL WASTE GLASS; CHROMIUM-OXIDE; RUTHENIUM DIOXIDE; NUCLEAR-WASTE; NOBLE-METALS; BEHAVIOR; VITRIFICATION; SOLUBILITY;

D O I：

10.1021/ic202156y

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Ruthenium, a fission product arising from the reprocessing of spent uranium oxide (UOX) fuel, crystallizes in the form of acicular RuO2 particles in high-level waste containment glass matrices. These particles are responsible for significant modifications in the physicochemical behavior of the glass in the liquid state, and their formation mechanisms are a subject of investigation. The chemical reactions responsible for the crystallization of RuO2 particles with acicular or polyhedral shape in simplified radioactive waste containment glass are described. In situ high-temperature environmental scanning electron microscopy (ESEM) is used to follow changes in morphology and composition of the ruthenium compounds formed by reactions at high temperature between a simplified RuO2 NaNO3 precursor and a sodium borosilicate glass (SiO2 B2O3 Na2O). The key parameter in the formation of acicular or polyhedral RuO2 crystals is the chemistry of the ruthenium compound under oxidized conditions (Ru-IV, Ru-V). The precipitation of needle-shaped RuO2 crystals in the melt might be associated with the formation of an intermediate Ru compound ((Na3RuO4)-O-V) before dissolution in the melt, allowing Ru concentration gradients. The formation of polyhedral crystals is the result of the direct incorporation of RuO2 crystals in the melt followed by an Ostwald ripening mechanism.

引用

页码：3478 / 3489

页数：12

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